CN1225047C - Battery - Google Patents

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Publication number
CN1225047C
CN1225047C CNB01802632XA CN01802632A CN1225047C CN 1225047 C CN1225047 C CN 1225047C CN B01802632X A CNB01802632X A CN B01802632XA CN 01802632 A CN01802632 A CN 01802632A CN 1225047 C CN1225047 C CN 1225047C
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China
Prior art keywords
extrudate
electric current
current collection
collection body
lubricant
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Expired - Fee Related
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CNB01802632XA
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Chinese (zh)
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CN1388997A (en
Inventor
伊格纳西奥·奇
乔治·辛特拉
让·高雷
格奥弗雷·西恩
马克·J·辛克莱尔
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Gillette Co LLC
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Gillette Co LLC
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Publication of CN1388997A publication Critical patent/CN1388997A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8864—Extrusion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8896—Pressing, rolling, calendering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making

Abstract

A method of making a cathode assembly for a metal-air battery includes extruding a composition having a catalyst, a fibrillatable material, and a lubricant, to form an extrudate, calendering the extrudate; connecting the extrudate to a current collector; and heating the extrudate to remove at least a portion of the lubricant to make the cathode assembly. The method can further include laminating a separator to the cathode assembly.

Description

Make the method for cell cathode assembly and metal-air battery
Technical field
The present invention relates to make the method for cell cathode assembly and metal-air cell.
Background technology
Battery generally is used as the energy.Battery comprises a negative electrode, is commonly referred to anode, and a positive electrode, is commonly referred to negative electrode.Anode contains the oxidized active material of energy; Negative electrode contains or consumes and can be reduced the intellectual material.In order to prevent the direct reaction of anode material and cathode material, anode and negative electrode are isolated from each other by a platy layer, and this platy layer is commonly called dividing plate.
When battery during as the electric energy in device, when for example being used for hearing aids or cell phone, antianode and negative electrode cause and electrically contact, and allow electron stream through this device and allow to take place separately oxidation and reduction reaction so that electric energy to be provided.The electrolyte that contacts with negative electrode with anode contains ion, and these ion flows are crossed interelectrode dividing plate, to keep the charge balance in the entire cell in discharge process.
In metal-air electrochemical primary cell, the material that cathode construction contains can react by catalytic oxidation-reduction, and this oxygen enters battery as the composition of air in the atmosphere by the inlet in the container.Form zinc oxide or zincate at anode.Like this, the whole electrochemical reaction in battery causes the zinc metal to be oxidized to zinc ion and is reduced into hydroxyl ion from the oxygen of air.When these chemical reactions took place, electronics was sent to negative electrode from anode, provides energy to device.
Summary of the invention
The present invention relates to make the method for metal-air battery cathode assembly.But this method comprises extruding and has catalyst fibrillation (fibrillatable) material, and the composition of lubricant, to form an extrudate; Roll this extrudate; This extrudate is linked to each other with an electric current collection body (collector); And to heat this extrudate be a part of lubricant to remove at least, thereby make cathode assembly.This method can further comprise with dividing plate and covers this cathode assembly.
This method can be used to produce thin, the high-intensity and negative electrode of (self-supporting) independently.This negative electrode can be made unified specification, so that the reliable battery performance to be provided.This negative electrode is flexible, allows to form the negative electrode of different shapes.
First-selected catalyst is a manganese dioxide.But fibrillation material at first is a polytetrafluoroethylene.Lubricant at first is isoparaffic solvent (iso-paraffinic solrent).
Extruding can with for example hammer ram or spiral shell rod be not less than room temperature or greater than the condition of room temperature under carry out.But the extruding to composition makes the effect of fibrillation material generation fibrillation, thereby produces high-intensity cathode assembly.
Extrudate is carried out spreading can be included under the condition that is higher than room temperature and allow extrudate pass through between pressure roller.These pressure rollers can be with identical speed motion, and perhaps with different speed, for example speed difference is 1.05-1.20: 1, and to form the negative electrode of asymmetric hardness.The spreading extrudate produces the negative electrode of thin unified specification, and it provides the reliable battery performance.Thin negative electrode allows to put into more active material (for example anode material) in battery, thereby increases the capacity of battery.
Can realize being connected of extrudate and electric current collection body by the electric current collection body being embedded extrudate, make that embedding the thickness that the electric current collection body is pressed into thing afterwards in extrudate can keep constant substantially.The electric current collection body is embedded extrudate can be realized by stream collection body of piezoelectricity between pressure roller and extrudate.
Can after being pressed into thin slice, heat extrudate.Extrudate is added heat energy from extrudate, remove whole lubricants basically.
On the other hand, the present invention relates to make a kind of method of metal-air battery, but comprise that extruding has the composition of catalyst fibrillation material and lubricant, to form an extrudate with negative electrode; Between pressure roller, roll this extrudate, and between the pressure roller this extrudate is being pressed onto on the electric current collection body.This method can comprise further that this extrudate of heating is a part of lubricant to remove at least.
On the other hand, the present invention relates to make a kind of method of metal-air battery.This method comprises: but form an extrudate by the composition that extruding has catalyst fibrillation material and a lubricant; Roll this extrudate; This extrudate is linked to each other with an electric current collection body; And to heat this extrudate be a part of lubricant to remove at least, thereby be made into cathode assembly; This cathode assembly is put into a shell, enter opening the air that enters shell is contacted with cathode assembly thereby this shell comprises air; One dividing plate is placed on adjacent cathodes assembly place; And an anode is placed on outside the contiguous dividing plate.This anode can comprise zinc.This catalyst can comprise the oxide of manganese.
Description of drawings
From description and accompanying drawing and accessory rights requirement, can more be clear that other characteristics of the present invention, purpose and advantage.
Accompanying drawing 1 is a block diagram of making cathodic process embodiment.
Embodiment
With reference now to accompanying drawing,, but the process of the cathode assembly of manufacturing battery comprises that formation has the cathode mix of catalyst fibrillation material and lubricant.This cathode mix is pressed to form extrudate (for example ribbon) by agent but the fibrillation material here can be by fibrillation.This extrudate is rolled with the thickness that reduces extrudate under heating condition and to remove from extrudate be a part of lubricant at least.Then, the extrudate that was rolled covers on the electric current collection body (for example net of Kuo Zhan metal or weaving), and to form cathode assembly, it is heated to remove more lubricant.Resulting cathode assembly can and be used for for example metal-air battery with a dividing plate and/or film covering.
But cathode mix comprises catalyst fibrillation material and lubricant.
The catalyst that is used for any traditional form of negative electrode can use.The example of catalyst comprises noble metal (for example PtPd and Ru); Argentum-based catalyzer, permanganate is (as AgMnO 4And KMnO 4) and the catabolite of metallic heterocyclic (heterocycle) (for example iron tetraphenylporphyrin (ironterrapheylporphyrin), cobalt tetramethyl hydroxy phenyl porphyrin (cobalt teramethoxy-phenylporphyrin), cobalt pthalocynanine, and iron pthalocynanine); And naphthenate (napthemates) (for example naphthenate of the naphthenate of cobalt and manganese).First-selected catalyst comprises the oxide of manganese, as MnO 2, MnO 3, and the hopcalite of manganese.The oxide of first-selected manganese is the synthetic manganese dioxide (EMD) of electrolysis, although the mixture of the manganese dioxide of chemical synthesis (CMD) and EMD and CMD also is available.The retail trader of these manganese dioxide comprises Kerr McGee company (Trona D), Chem Metals company, Tosoh, Delta Manganess, Mitsui Chemicals and JMC.In addition, but can also reach the fibrillation mixtures of material, form the oxide of the manganese in the cathode mix on the spot by nitrate, the carbon that decomposes manganese.Usually, negative electrode for example comprises by weight and to be the manganese dioxide between about 5% and about 20%.
Carbon also is to be any traditional carbon that uses in the negative electrode.In cathode mix, add carbon effective electronic conductivity is provided.Carbon also as the place of hydrogen reduction and thereon deposited catalyst with the place of peroxide in minute electrolytic cell.At first carbon is carbon black, the example of spendable carbon include but not limited to Black Pearls2000 (Cabot, Billerica, MA) Vulcan XC-72 (Cabot), Monarch 1300, Shawinigan Black, Printex, Ketjen Black and PWA.Usually, negative electrode comprises for example being carbon granule between 10% and 90% by weight, preferably between about 30% and about 70%, more preferably about 40%.
But cathode mix comprises the fibrillation material, and when they were stressed, for example the extruding force in extrusion process just formed fiber under mold pressing or the effect of rolling, or the fibrillation effect takes place.But do the time spent when fibrillation material generation fibrillation, it can strengthen cathode mix.But the fibrillation examples of material is a polytetrafluoroethylene (PTFE), can (Wilmington Delaware) obtains from DuPont.Usually, but cloudy and for example comprise the fibrillation material between 10% to about 90% by weight, between preferred 20% to about 80%, more preferably between about 45% to 50%.
But can select different fibrillation materials with control fibre strength or original fiber degree.Usually, but HMW fibrillation material energy fibrillation is very fast, and can produce stronger fiber and/or more fiber.But low-molecular-weight fibrillation material forms short and more weak fiber usually, and it can make to handle and be easier to.For example, compare, the roll (hereinafter describing) that may not can than the negative electrode of short fiber stops up rcc system is arranged with having more long stapled negative electrode.
Lubricant or solution are used for making cathode mix that enough lubrifications be arranged in extrusion process (hereinafter describing).The example of lubricant comprises fatty solution, (dearomatijed) aliphat of removing aromatization, and alcohols (for example isopropyl alcohol and butanols).Phthalic acid salt, ether, ester class acid amides and ketone also can use.Preferred emollient is an iso-alkane solution, as Isopar, can obtain from Exxon (NewJersey).Usually, negative electrode comprises by weight the lubricant for about 10% to about 80%, and for example per 1 gram carbon black (Vulcan XC-72) has 1.66 gram Isopar.Yet optimized lubricant concentration is the function of the type of used carbon.For example, if the carbon in the cathode mix has high surface area or lubricant is had high absorption figure (for example Black Pearl 2000), the carbon that the lubricant that may need is low more than those surface areas or absorption affinity is low (for example Valcan carbon black) then, other character of carbon also can influence the concentration of lubricant in the cathode mix.For example, the lubricant of HMW is usually than low-molecular-weight lubricant toughness more.The lubricant of HMW also has high volatilization temperature usually, and they can allow high treatment temperature and long resident or processing time, but may be difficult to remove from cathode mix.
Cathode mix thoroughly mixes in for example two-orbit (double plantary) mixer (as the Ross mixer) usually.The example of cathode mix comprises 11.2%Mn 2O 3, 40.8% carbon, and 48%PTFE; And 12.23%M nO 2, 40.3% carbon and 47.43%PTFE are about 40% IsoparG by weight to their interpolations.Mixing time is the function of mixture amount, is generally 5 masters 30 minutes.
But mixed cathode mix is subjected to shear pressure or make it stressed so that the effect of fibrillation material generation fibrillation.Usually, cathode mix is by piston extruding formation extrudate (for example ribbon or pearl (bead) shape thing) thereby by fibrillation.The about usually 35-40 mil of the thickness of extrudate.Reduce in scale, promptly the long-pending ratio with the mould outlet sectional area of extruder barrel body section is about 140 to 1, and also available certainly other ratios were as 90: 1 to 140: 1.Usually, high reduce in scale provides high original fiber degree.The piston extruding is disclosed in " plastics extrusion technique ", editor F.Hensen, and the Oxford University Press, 1988, be incorporated herein by reference here.Extruding can for example carried out in the heated mould, its temperature at 5 ℃ between 400 ℃.Being higher than room temperature pushes and can increase original fiber degree.Can use other extrusion techniques.For example, may use continuously extruded technology, come with single-screw or double-screw extrusion machine, continuous mixer, continuous processor, reciprocating type rubbing mixer and other continuous mixing arrangements, these devices can directly be presented extrudate to rcc system.
By extrudate is passed between two backwards rotation milling rollers of constant spacing (for example about 2 mils to about 20 mils), extrudate is rolled, it is thin that this forms negative electrode, homogeneous with flexibility.Usually, extrudate (is generally 30 ℃ to 300 ℃) and is rolled under heating condition, but this can strengthen the fibrillation effect of fibrillation material.Along with increasing of roller temperature, but making the temperature of extrudate be higher than the softening temperature of fibrillation material, is 66 °F to PTFE for example, and then negative electrode may further be ground thin and can not produce defective in negative electrode.For example, at room temperature rolling extrudate allows negative electrode to be rolled about 10 mil thick usually and does not have and tear, but for essentially identical condition, can produce the negative electrode of about 3-10 mil thick and do not have and tear for example rolling under 80 ℃, the fibrillation effect that strengthens can also change the physical property of negative electrode, for example tensile strength, ultimate elongation and stretch modulus.Pressure roller normally has core, with the portion's circulation within it of permission heat transfer medium, thereby is passed in the temperature profile that roller surface has homogeneous.
Under heating condition, roll the lubricant content that can reduce in the negative electrode.For example, that lubricant concentration is reduced to from about 40% is about 30% owing to mechanically extrude lubricant to roll common meeting under heating state not, rolls to make lubricant concentration reduce to about 20% from about 40% under heating state.The lower negative electrode that lubricant concentration provided makes the robustness (consistency) that negative electrode combines with the electric current collection body in lamination process (hereinafter describing) good.For example, the negative electrode of doing usually with the stack of electric current collection body, and wet negative electrode usually and the electric current collection body electrically contact poor.Believe that lubricant allows in the cinclides of cathode system and electric current collection body.
Roll and to repeat until forming desirable negative electrode.Usually, can allow extrudate repeatedly roll by one group of pressure roller.The practice that substitute or that replenish is: extrudate can be disposable by the rcc system of many group pressure rollers is arranged.Roll negative electrode by many groups pressure roller and can produce high compaction, good homogeneity and battery performance carried out better quality control.
Milling roller can rotate or rotate with friction speed with identical speed.The speed control of pressure roller is given the cross section of negative electrode, so can reconcile the negative electrode physical property that causes.Usually, the velocity of rotation of increase pressure roller then increases the hardness of negative electrode.If two pressure rollers rotate with identical speed, then cross section and hardness are symmetrical.If use different speed, for example speed difference be 1.05-1.20 than 1, then cross section and hardness are asymmetric, it can be used to make negative electrode and enables to stack with electric current collection body optimal layer, as described in hereinafter.Like this, a side of negative electrode can be softer than opposite side, and a softer side can be stacked together with the electric current collection body.The about usually 2ft/min of the speed of pressure roller is to about 50ft/min.In addition, pressure roller can be made into taper to promote the cross-linked of fiber, and this can strengthen the intensity of negative electrode, toughness and flexibility.After negative electrode was fed by the taper pressure roller, this negative electrode can be fed by not making tapered pressure roller, to produce the negative electrode of homogeneous thickness.
Extrudate is accelerated the thickness that the speed of sending into milling roller also can control cathode.Along with the increase of acceleration, the linear velocity by increasing pressure roller and/or reduce the pressure roller diameter for example, then hardness is increased.Have, the slit between the scalable pressure roller influences the physical property of negative electrode again.Usually, the slit produces harder negative electrode more closely, because pressure roller has applied bigger power on negative electrode, this can cause bigger fibrillation effect.
Usually,, make the extrudate that rolled be laminated to vegetables and be embedded in the electric current collection body, to form cathode assembly by allowing negative electrode and electric current collection body pass one group of pressure roller.This electric current collection body can be nickel plating carbon steel knitmesh for example 5 mil thick, weaving (GDC, Hanover, PA) and the nickel metal collection body that launches (Delker company, Branford, CT).Usually, pressure roller rotates with identical speed, and for example per minute is 2 feet.Stacked can at high temperature carrying out, improved contact between negative electrode and the electric current collection body to move to lubricant on negative electrode/electric current collection body interface by volatilization by for example about 30 ℃ to about 300 ℃.Preferably cathode assembly and the stacked extrudate that rolled before have essentially identical thickness and length (for example 〉=90% original thickness and length).The constant electric current collection body that shows of thickness or length is embedded negative electrode fully, and negative electrode is distorted.Preferably, in case stacked together, negative electrode just can not remove from the electric current collection body, and in other words, this negative electrode will be torn before removing lamination.
Then, but preferably make cathode assembly heating from the fibrillation material, to remove remaining lubricant.For example, heating can be preferably 150 ℃ at about 60-300 ℃, carries out in the category-A stove about 2 hours; Carried out in a vacuum about 2 hours at about 60 ℃ to about 300 ℃; Or about 60 ℃ to about 300 ℃ carried out about 2 hours under inert gas (for example nitrogen or argon) in convection furnace.This cathode assembly also can further be heated in additional heating steps, for example under about 300 ℃ of situations, but from the fibrillation material, further to remove surfactant.
The cathode assembly that the result forms is flexible, independent structures, has the surface texture of porous, as seeing under in scanning electron microscopy.Cathode assembly has fiber, the trend of its fiber with pressed direction or conveyer belt direction identical firmly.
Cathode assembly can be stacked with film and/or dividing plate, and the show off film is the thick ventilative material of 0.1-0.2mm for example, as PTFE, is used for limit electrolysis liquid and spills battery.Dividing plate is used to make cathode assembly and anode electric insulation, thereby can not take place to cause battery short circuit owing to negative electrode directly contacts with anode.That this dividing plate is generally is 0.05 to 0.08mm thick, is generally porous, the polymer of electric insulation, (Celgard 5550, Celanese (Summit, New as polypropylene, Jersey)) or polyvinyl alcohol (PVA), its allows the electrolyte in anode material to contact with negative electrode.The another kind of practice is to use dividing plate at the scene.For example, with having defoaming agent and bactericide in case the 5-20%PVA aqueous solution coating cathode of organic substance growth and in about 60 ℃ of dried cathode can be split into the thick solid PVA film of 0.05-0.1mm.The description that the dividing plate of coating is at the scene done sees for example United States Patent (USP) Shen U.S.S.N.09/280367, accepts on March 29th, 1999, is incorporated herein by reference here.
Stacked cathode assembly can be used to form metal-air battery, as at U.S. Patent application U.S.S.N.09/374, and 227 (on August 13rd, 1999 accepted); U.S.S.N.09/374,278 (on August 13rd, 1999 accepted); And U.S.S.N.09/427, as described in 371 (on October 26th, 1999 accepted), these applications here are introduced into as a reference.
Example 1
Have 13% manganese dioxide-catalyst, cathode mix and the 40%Isoper G lubricant of 40% carbon (Vulcan XC-72) and 47%PTFE stirred in planetary stirring machine 5 minutes.The mixture of cathode mix and lubricant is loaded in the piston extrusion machine and carried out under 500psi pressure 2 minutes.This mixture is compressed to remove air and cavity in the process of carrying out.
Mixture is extruded by 2 inches wide moulds, cause 140: 1 reduce in scale, to form extrudate, the temperature of mould is a room temperature, although because extrusion process mould is heated reaches 30 ℃ of piston speeds are 3in/min, the scope of the back pressure in extrusion process strong (back pressure) is 5000 to 5,700pSi.
Extrudate is rolled at 80 ℃, and the about 4ft/min of barrel velocity reaches target thickness 10 mils.Roll at this and to lose a semi-lubricant in step, cause lubricant concentration to be about 20%.
On the Fenn roller, the extrudate that rolls by the prestrain pressure roller and on electric current collection body top makes the extrudate that rolled be layered in the nickel metal electric current collection body (Delker3Ni5-050, be stretched and rolled) of expansion.Barrel velocity is about 2.6ft/min.
This negative electrode in air in Daspatch category-A stove 150 ℃ the oven dry 2 hours to remove unnecessary solvent.This negative electrode is laminated on dividing plate and the PTFE film, and is included into and is of a size of weakness-air button of No. 13.
Example 2
Piston pressed against cathode mixture makes it pass through the garden cylindrical die as described above, thereby makes garden tubular negative electrode.About 90 ℃ of mold temperature.The garden tube that is squeezed out has wall thickness about 0.020 ", its overall diameter about 0.430 ".This garden tube is independently, and is compressible, and can be cut.Can be by stacked on negative electrode or weaving lead, nickel wire is for example realized being connected of electric current collection body and negative electrode.
Example 3
Form the double-layer hollow electrode assemblie with following method.Form the negative electrode of 10 mil thick by above-mentioned extruding and the process of rolling.By pushing and rolling the voided layer that forms 10 mil thick, 70%PTFE and 30% carbon (Vvlcan XC72) are arranged wherein.This negative electrode and voided layer are stacked together between pressure roller to reach 10 final mil thickness, to form two-layer electrode.The electric current collection body is layered in voided layer one side of two-layer electrode, to form the two-layer electrode assembly.This assembly is dried 6 hours to remove lubricant at 60 ℃.
This component table reveals good release-resistance, good polarization performance and flexibility.Under sem analysis, this component table reveals does not have seam or crack between the different layers.The air permeability of this assembly is 80-100Gurley-sec, and being that 10cc is empty here intended by 1 square inch of time that sample is used.
Just estimate in test battery with the negative electrode that said process is made, battery is increased gradually and is write down cell voltage in this test battery.The performance of these negative electrodes is similar to the cathode performance made from traditional dry coating (dry coating).
Some embodiment of the present invention have been described.However, will be understood that, can carry out various modifications and do not leave the spirit and scope of the present invention.For example, although description of the invention relates to is metal-air battery, other air cathodes that use in using that the present invention can also be applied to fuel cells applications or air cathode arranged.

Claims (31)

1. make a kind of method of cathode assembly, this method comprises:
But extruding comprises the composition of catalyst fibrillation material and lubricant, to form extrudate;
Roll this extrudate;
This extrudate is combined with the electric current collection body; And
This extrudate is heated to temperature between 60 ℃ to 300 ℃, to remove at least a portion lubricant.
2. the method for claim 1 further comprises carrier ring is laminated on the cathode assembly.
3. the method for claim 1, described extruding to composition is undertaken by the piston extruding.
4. the method for claim 1, described extruding to composition is carried out between 20 ℃ and 300 ℃.
5. the method for claim 1, described extruding to composition is undertaken by continuously extruded.
6. the method for claim 1, described catalyst is the compound of manganese.
7. the method for claim 6, the compound of described manganese is selected from and comprises Mn 2O 3, Mn 3O 4And MnO 2One group of compound.
8. the method for claim 1, but described fibrillation material has contained polytetrafluoroethylene.
9. the method for claim 1, described lubricant is selected from aliphat solution, aromatic solvent, removes aromatized fat family solution, alcohols, phthalic acid salt, ether, ester class, acid amides and ketone.
10. the method for claim 1, described lubricant comprises iso-alkane solution.
11. the method for claim 10, described composition comprise 10% to 90% iso-alkane solution by weight.
12. the method for claim 1, described rolling of extrudate is included in pressed this extrudate between the pressure roller.
13. the method for claim 12, described composition comprise 40% iso-alkane solution by weight.
14. the method for claim 12, described pressure roller is with different speed motions.
15. the method for claim 14, described pressure roller are with speed difference 1.05-1.20: 1 motion.
16. the method for claim 12, described pressure roller is heated to 30 ℃ to 300 ℃ temperature.
17. the method for claim 12, described pressure roller becomes taper.
18. the method for claim 1, described extrudate comprised with being connected of electric current collection body the electric current collection body is embedded this extrudate.
19. the method for claim 16, embedding the electric current collection body is to carry out under the temperature between 30 ℃ to 300 ℃.
20. the method for claim 18, described after embedding the electric current collection body thickness of this extrudate be reduced.
21. the method for claim 18, described after embedding the electric current collection body thickness of this extrudate remain unchanged.
22. the method for claim 18, pass through electric current collection body and extrudate described electric current collection body embedding extrudate is comprised between pressure roller.
23. the method for claim 1, described heating to extrudate is carried out in a vacuum.
24. the method for claim 1, described heating to extrudate comprises the temperature that is heated between 100 ℃ to 300 ℃.
25. the method for claim 1, whole lubricants are removed in described heating to extrudate.
26. the method for claim 1 further comprises: after step, this extrudate is included in metal-air battery to the extrudate heating.
27. the method for claim 1 further comprises: after to the extrudate heating, this extrudate is included in fuel cell.
28. make a kind of method of metal-air battery, this method comprises:
Method according to claim 1 is made cathode assembly;
This cathode assembly is put into a shell, enter opening the air that enters shell is contacted with cathode assembly thereby this shell comprises air;
One dividing plate is placed on adjacent cathodes assembly place; And
One anode is placed on contiguous dividing plate place.
29. the method for claim 28, described anode comprises zinc.
30. the method for claim 28, described catalyst comprises the oxide of manganese.
31. the method for claim 28, described catalyst are selected from one group, wherein comprise the catabolite of noble metal, argentum-based catalyzer, permanganate, metallic heterocyclic and the catabolite of naphthenate.
CNB01802632XA 2000-03-23 2001-03-09 Battery Expired - Fee Related CN1225047C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/532,280 2000-03-23
US09/532,280 US6368365B1 (en) 2000-03-23 2000-03-23 Method of making a battery

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Families Citing this family (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6627252B1 (en) 2000-05-12 2003-09-30 Maxwell Electronic Components, Inc. Electrochemical double layer capacitor having carbon powder electrodes
WO2002067628A1 (en) * 2001-02-17 2002-08-29 Oticon A/S Communication device for mounting on or in the ear
EP1393393B1 (en) * 2001-05-24 2011-05-11 Rayovac Corporation Ionically conductive additive for zinc-based anode in alkaline electrochemical cells
DE10148599A1 (en) 2001-10-02 2003-04-10 Bayer Ag Production of foil, used in production of gas diffusion electrodes for producing chlorine and caustic soda, involves rolling dry powder mixture of foil material while maintaining roll gap during rolling process
US6643119B2 (en) 2001-11-02 2003-11-04 Maxwell Technologies, Inc. Electrochemical double layer capacitor having carbon powder electrodes
EP1479119B1 (en) * 2002-03-07 2012-08-01 Bathium Canada Inc. Positive electrode films for alkali metal polymer batteries and method for making same
US20040229116A1 (en) * 2002-05-24 2004-11-18 Malinski James Andrew Perforated separator for an electrochemical cell
US20040086774A1 (en) * 2002-11-05 2004-05-06 Munoz Beth C. Gas diffusion electrodes
US20040157101A1 (en) * 2003-02-11 2004-08-12 Smedley Stuart I. Fuel cell electrode assembly
US7352558B2 (en) 2003-07-09 2008-04-01 Maxwell Technologies, Inc. Dry particle based capacitor and methods of making same
US7791860B2 (en) 2003-07-09 2010-09-07 Maxwell Technologies, Inc. Particle based electrodes and methods of making same
US7585579B1 (en) 2003-07-29 2009-09-08 The United States Of America As Represented By The Secretary Of The Army Electrolyte for metal-oxygen battery and method for its preparation
US7147967B1 (en) 2003-07-29 2006-12-12 The United States Of America As Represented By The Secretary Of The Army Cathode for metal-oxygen battery
TW200520292A (en) 2003-08-08 2005-06-16 Rovcal Inc High capacity alkaline cell
CN101577347B (en) * 2003-08-18 2012-05-30 鲍尔热尼系统公司 Method for manufacturing nickel zinc batteries
US7920371B2 (en) 2003-09-12 2011-04-05 Maxwell Technologies, Inc. Electrical energy storage devices with separator between electrodes and methods for fabricating the devices
US7279250B2 (en) * 2003-11-24 2007-10-09 The Gillette Company Battery including aluminum components
US7544384B2 (en) * 2003-11-24 2009-06-09 The Gillette Company Methods of making coated battery components
US7090946B2 (en) 2004-02-19 2006-08-15 Maxwell Technologies, Inc. Composite electrode and method for fabricating same
US20050242471A1 (en) * 2004-04-30 2005-11-03 Bhatt Sanjiv M Methods for continuously producing shaped articles
AR047875A1 (en) 2004-06-04 2006-03-01 Rovcal Inc ALKAL CELLS THAT PRESENT HIGH CAPACITY
US7440258B2 (en) 2005-03-14 2008-10-21 Maxwell Technologies, Inc. Thermal interconnects for coupling energy storage devices
US8703330B2 (en) * 2005-04-26 2014-04-22 Powergenix Systems, Inc. Nickel zinc battery design
US7572551B1 (en) 2005-06-27 2009-08-11 Greatbatch Ltd. Electrode active blanks and methods of making
CN101326675B (en) * 2005-12-06 2012-06-06 雷沃尔特科技有限公司 Bifunctionan air electrode
US8133615B2 (en) * 2006-06-20 2012-03-13 Eveready Battery Company, Inc. Alkaline electrochemical cell
WO2009123888A1 (en) * 2008-04-02 2009-10-08 Powergenix Systems, Inc. Cylindrical nickel-zinc cell with negative can
US8123739B2 (en) * 2008-08-19 2012-02-28 Cook Medical Technologies Llc Drainage catheter and method for catheterizing a patient
WO2011013005A1 (en) * 2009-07-31 2011-02-03 Revolt Technology Ltd. Metal-air battery with ion exchange material
US20110236798A1 (en) * 2010-02-12 2011-09-29 Revolt Technology Ltd. Manufacturing methods for air electrode
US20110236772A1 (en) * 2010-02-12 2011-09-29 Revolt Technology Ltd. Manufacturing methods for air electrode
WO2013036802A1 (en) 2011-09-07 2013-03-14 24M Technologies, Inc. Stationary semi-solid battery module and method of manufacture
US9401501B2 (en) 2012-05-18 2016-07-26 24M Technologies, Inc. Electrochemical cells and methods of manufacturing the same
US9590233B2 (en) 2013-04-05 2017-03-07 Duracell U.S. Operations, Inc. Method of making a cathode
DE102014218993A1 (en) 2014-09-22 2016-03-24 Robert Bosch Gmbh Separator cathode current collector element
US10637038B2 (en) 2014-11-05 2020-04-28 24M Technologies, Inc. Electrochemical cells having semi-solid electrodes and methods of manufacturing the same
JP6789938B2 (en) 2015-06-18 2020-11-25 ２４エム・テクノロジーズ・インコーポレイテッド２４Ｍ Ｔｅｃｈｎｏｌｏｇｉｅｓ， Ｉｎｃ． Single pouch battery cell and its manufacturing method
CN106785241B (en) * 2016-12-16 2019-04-12 中国科学院宁波材料技术与工程研究所 Metal air battery cathodes and preparation method thereof
DE102017208220A1 (en) * 2017-05-16 2018-11-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Process for producing a dry film and dry film and dry film coated substrate
US11742525B2 (en) 2020-02-07 2023-08-29 24M Technologies, Inc. Divided energy electrochemical cell systems and methods of producing the same
US11462724B1 (en) 2021-05-13 2022-10-04 ZAF Energy Systems, Incorporated Electrode manufacturing
US11205772B1 (en) * 2021-05-13 2021-12-21 ZAF Energy Systems, Incorporated Zinc electrode manufacturing
WO2023212159A1 (en) * 2022-04-27 2023-11-02 ZAF Energy Systems, Incorporated Electrode manufacturing

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4121020A (en) 1977-01-21 1978-10-17 Gte Laboratories Incorporated Ultra-thin button-type primary electrochemical cell
FR2468218A1 (en) 1979-10-18 1981-04-30 Alsthom Cgee METHOD OF MANUFACTURING BY CALENDERING POROUS THIN STRIPS AND PRODUCTS OBTAINED, ESPECIALLY ELECTRODES FOR FUEL CELLS
US4385019A (en) 1981-01-19 1983-05-24 Mpd Technology Corporation Production of a polymeric active composition
US4320184A (en) 1981-01-19 1982-03-16 Mpd Technology Corporation Production of a cell electrode system
US4320185A (en) 1981-01-19 1982-03-16 Mpd Technology Corporation Production of a cell electrode system
FR2503936B1 (en) * 1981-04-13 1985-11-08 Wonder PROCESS FOR PREPARING CURRENT COLLECTORS FOR ELECTROCHEMICAL DEVICES, BY DEPOSITION ON ELECTRODES FOR SUCH DEVICES, AND ELECTRODELECTOR COLLECTOR ASSEMBLIES OBTAINED BY THIS PROCESS
EP0063981B1 (en) 1981-04-13 1987-11-11 Societe Les Piles Wonder Method of manufacturing thin electrodes, particularly gas electrodes, for electrochemical devices, and thin electrodes obtained by such a method, the electrodes possibly being provided with current collectors
US4457953A (en) 1981-12-23 1984-07-03 The Dow Chemical Company Electrode material
US4556618A (en) 1983-12-01 1985-12-03 Allied Corporation Battery electrode and method of making
JPS61230266A (en) * 1985-04-05 1986-10-14 Asahi Glass Co Ltd New gas diffusion electrode
JPS61239566A (en) * 1985-04-16 1986-10-24 Asahi Glass Co Ltd Improved gas diffusion electrode
JPS6348753A (en) * 1986-08-14 1988-03-01 Fuji Electric Co Ltd Manufacture of electrode catalyst layer for fuel cell
JPS63187574A (en) * 1987-01-29 1988-08-03 Japan Gore Tex Inc Fuel cell electrode-matrix monobloc forming and its manufacture
JPH04215255A (en) * 1990-12-14 1992-08-06 Fuji Electric Co Ltd Manufacture of electrode for fuel cell
US5304431A (en) * 1992-05-20 1994-04-19 Schumm Jr Brooke Fluid depolarized electrochemical battery with automatic valve
US5242765A (en) 1992-06-23 1993-09-07 Luz Electric Fuel Israel Limited Gas diffusion electrodes
US5393617A (en) 1993-10-08 1995-02-28 Electro Energy, Inc. Bipolar electrochmeical battery of stacked wafer cells
US5435874A (en) 1993-11-01 1995-07-25 Wilson Greatbatch Ltd. Process for making cathode components for use in electrochemical cells
US5441823A (en) 1994-07-01 1995-08-15 Electric Fuel (E.F.L.) Ltd. Process for the preparation of gas diffusion electrodes
US6054230A (en) * 1994-12-07 2000-04-25 Japan Gore-Tex, Inc. Ion exchange and electrode assembly for an electrochemical cell
JPH08264186A (en) * 1995-03-28 1996-10-11 Matsushita Electric Ind Co Ltd Cylindrical air zinc battery

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US6368365B1 (en) 2002-04-09
AU2001243525A1 (en) 2001-10-03
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